JP2006249370A - Metal working oil composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metal working oil composition capable of achieving a working performance at a high level without using a chlorine-based extreme-pressure agent. <P>SOLUTION: The metal working oil composition comprises a hydrocarbon oil and 1-50 mass% of a cycloaliphatic polycarboxylate compound based on the total amount of the composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to metalworking oil compositions.

  Conventionally, in the field of metal processing, chlorine-based extreme pressure agents such as chlorinated paraffin, and sulfur-based extreme pressure agents such as sulfurized fats and oils and polysulfides are frequently used. In particular, shaving processing, deep hole processing (BTA processing, gun drill processing), automatic lathe processing, broaching processing, difficult processing such as thread rolling processing, or heavy processing, or heat-resistant alloys such as stainless steel and Inconel were used as the work material. The use of chlorinated extreme pressure agents is indispensable for processing difficult-to-process materials.

  On the other hand, there are concerns about the carcinogenicity of some chlorinated paraffins or the generation of dioxins when incinerating chlorinated waste liquids.

Accordingly, development of new metalworking oils that do not use chlorinated extreme pressure agents is being promoted. For example, Patent Document 1 discloses a metal processing oil in which a sulfur-based extreme pressure agent and sulfonates are used in combination, and the use of such a metal processing oil is equivalent to or more than when a chlorine-based additive is used. It is shown that processing performance can be obtained.
JP-A-6-158074

  However, there is room for further improving the processing performance of the conventional metal processing oil. In particular, in the fields of heavy processing, difficult processing, difficult-to-process material processing, etc., metal processing has been performed because of the fact that the processing conditions have become more severe in recent years and the development of new work materials has been promoted. The required performance for oil is getting higher and higher. Moreover, it is desirable that it is metal processing oil excellent in biodegradability from the point of a waste treatment or a work environment.

  The present invention has been made in view of such circumstances, and provides a metalworking oil composition capable of achieving a high level of processing performance without using a chlorine-based extreme pressure agent. Objective. It is another object of the present invention to provide a metalworking oil composition that is highly biodegradable and environmentally friendly.

  As a result of intensive studies to achieve the above object, the present inventors have solved the above problems by using a metalworking oil composition containing a predetermined amount of an alicyclic polyvalent carboxylic acid ester compound as a hydrocarbon oil. As a result, the present invention has been completed.

  That is, the metalworking oil composition of the present invention is characterized in that the hydrocarbon oil contains 1 to 50% by mass of the alicyclic polyvalent carboxylic acid ester compound based on the total amount of the composition.

  According to the metalworking oil composition of the present invention, by having the above configuration, the machining performance can be sufficiently enhanced without using a chlorinated extreme pressure agent, so that the machining efficiency is improved and the tool life is improved. In addition, it is possible to achieve a high level and good balance in handling.

  According to the present invention, there is provided a metal working oil composition capable of achieving a high level of processing performance without using a chlorine-based extreme pressure agent.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

  The hydrocarbon oil contained in the metalworking oil composition of the present invention may be either mineral oil or synthetic oil, or a mixture thereof.

  As the mineral oil used in the present invention, for example, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and vacuum distillation is subjected to solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, Paraffinic mineral oil or naphthenic mineral oil refined by appropriately combining refining treatments such as catalytic dewaxing, hydrorefining, sulfuric acid washing, and clay treatment can be mentioned.

  Specific examples of the synthetic oil used in the present invention include propylene oligomer, polybutene, polyisobutylene, 1-octene oligomer, 1-decene oligomer, ethylene and propylene co-oligomer, ethylene and 1-octene. Co-oligomers, poly-α-olefins such as ethylene and 1-decene co-oligomers or their hydrides; isoparaffins; alkylbenzenes such as monoalkylbenzenes, dialkylbenzenes, polyalkylbenzenes; monoalkylnaphthalenes, dialkylnaphthalenes, polyalkylnaphthalenes, etc. These may be used alone or in combination of two or more.

  The content of the hydrocarbon oil in the metalworking oil of the present invention is 50 to 99% by mass, preferably 60 to 95% by mass, and more preferably 70 to 90% by mass based on the total amount of the composition. preferable.

The alicyclic polyvalent carboxylic acid ester compound used in the present invention has at least two ester groups represented by the alicyclic ring and the following general formula (a).
-COOR (A)
[In formula (a), R represents a C1-C30 hydrocarbon group, and R of each ester group may be the same or different. ]

  Examples of the alicyclic ring of the alicyclic polyvalent carboxylic acid ester compound according to the present invention include a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring, a cycloheptene ring, and the like. A cyclohexene ring is preferred. Among these, from the viewpoints of high oxidation stability and low extractability of organic materials, an alicyclic ring having no double bond is preferable, and a cyclohexane ring is more preferable.

  As described above, the alicyclic polyvalent carboxylic acid ester compound has at least two ester groups. When the number of ester groups is one, heat / hydrolysis stability is insufficient, which is not preferable. The number of ester groups is not particularly limited, but is preferably 4 or less, more preferably 3 or less, and still more preferably 2 from the viewpoint of low temperature fluidity.

  In addition, at least two of the ester groups represented by the formula (a) are preferably bonded to adjacent carbon atoms on the alicyclic ring. In the case where they are not bonded to adjacent carbon atoms on the alicyclic ring, the thermal / hydrolytic stability is insufficient, which is not preferable.

  Furthermore, the steric configuration of the ester group represented by the formula (a) is not particularly limited, and the two carboxyl groups bonded to adjacent carbon atoms on the alicyclic ring may be either a cis isomer or a trans isomer. May be. Moreover, any one of cis isomers and trans isomers among aliphatic cyclic polycarboxylic acids may be used alone, or a mixture of cis isomers and trans isomers may be used. However, from the viewpoint of heat / hydrolysis stability, a cis body is preferable, and from the viewpoint of achieving both heat / hydrolysis stability and lubricity, a trans body is preferable. Further, when a cis isomer and a trans isomer are mixed and used, the molar ratio is preferably 20/80 to 80/20, more preferably 25/75 to 75/25, still more preferably 30/70 to 70/30. It is. When the molar ratio of the cis form to the trans form is within the above range, the thermal / hydrolysis stability tends to be compatible at a higher level.

  R in the formula (a) represents a hydrocarbon group having 1 to 30 carbon atoms, preferably 2 to 24 carbon atoms, more preferably 3 to 18 carbon atoms. Examples thereof include an alkyl group, an alkylcycloalkyl group, an aryl group, an alkylaryl group, and an arylalkyl group. Among these, an alkyl group, a cycloalkyl group, or an alkylcycloalkyl group is preferable from the viewpoint of heat / hydrolysis stability.

  The alkyl group may be linear or branched. Examples of the alkyl group having 3 to 18 carbon atoms include a linear or branched propyl group, a linear or branched butyl group, a linear or branched pentyl group, a linear or Branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched decyl group , Linear or branched undecyl group, linear or branched dodecyl group, linear or branched tridecyl group, linear or branched tetradecyl group, linear or branched Examples thereof include a branched pentadecyl group, a linear or branched hexadecyl group, a linear or branched heptadecyl group, and a linear or branched octadecyl group.

Among these, a straight chain is preferable from the viewpoint of biodegradability and lubricating performance, and a branched chain is preferable from the viewpoint of hydrolysis stability and low temperature characteristics. Accordingly, those having both a straight chain and a branched chain are preferred. In order to satisfy both advantages in a well-balanced manner, the ratio of the straight chain to the branched chain is preferably 20:80 to 80:20, more preferably 30:70 to 70:30. More preferably, it is 40: 60-60: 40.
Also, the longer the carbon chain, the better the lubrication performance and the lower the extractability of the organic material.

  Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and the like, and a cyclohexyl group is preferable from the viewpoint of thermal and hydrolytic stability. The alkylcycloalkyl group is a group in which an alkyl group is bonded to a cycloalkyl group, but is preferably a group in which an alkyl group is bonded to a cyclohexyl group from the viewpoint of thermal and hydrolytic stability. Further, the alkylcycloalkyl group preferably has a total carbon number of 6 or more from the viewpoint of thermal and hydrolytic stability, and preferably has a total carbon number of 10 or lower from the viewpoint of low-temperature fluidity.

  Of course, as the alicyclic polyvalent carboxylic acid ester compound, one or more hydrocarbon groups may be bonded to the carbon atom on the alicyclic ring. As such a hydrocarbon group, an alkyl group is preferable, and a methyl group is particularly preferable.

  The alicyclic polyvalent carboxylic acid ester compound referred to in the present invention has the above-mentioned structure. Such an ester compound is prepared by combining a predetermined acid component and an alcohol component according to a conventional method, preferably nitrogen or the like. It is prepared by esterification under heating in an atmosphere of an inert gas, in an atmosphere of an esterification catalyst or in the absence of a catalyst. Here, from the viewpoint of heat and hydrolysis stability, it is preferable to prepare by an esterification reaction without a catalyst.

  Examples of the acid component of the alicyclic polycarboxylic acid ester compound include cycloalkane polycarboxylic acid, cycloalkene polycarboxylic acid, and acid anhydrides thereof. Among them, at least two of the ester groups are on the alicyclic ring. Those bonded to carbon atoms adjacent to each other are preferably used. These can be used as one kind or a mixture of two or more kinds. Specifically, 1,2-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 1-cyclohexene-1,2-dicarboxylic acid, 3-methyl-1,2-cyclohexanedicarboxylic acid, 4-methyl -1,2-cyclohexanedicarboxylic acid, 3-methyl-4-cyclohexene-1,2-dicarboxylic acid, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1 2,4,5-cyclohexanetetracarboxylic acid and acid anhydrides thereof. Among these, from the viewpoint of suppressing an increase in viscosity when the prepared ester compound is used under long-term or severe conditions, 1,2-cyclohexanedicarboxylic acid, 3-methyl-1,2-cyclohexanedicarboxylic acid, 4 Preferred are methyl-1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid and their anhydrides, while long-term or harsh conditions 4-cyclohexene-1,2-dicarboxylic acid, 1-cyclohexene-1,2-dicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid from the viewpoint of suppressing an increase in the total acid value during use in 3-methyl-4-cyclohexene-1,2-dicarboxylic acid, 4-methyl-4-cyclohexene-1, - dicarboxylic acids and anhydrides thereof are preferred.

  There is no restriction | limiting in particular in the manufacturing method of these alicyclic polyhydric carboxylic acid and its anhydride, What was obtained by arbitrary methods can be used. Specifically, cis-4-cyclohexene-1,2-dicarboxylic acid can be obtained by reacting butadiene and maleic anhydride in a benzene solvent at 100 ° C.

  As the alcohol component of the alicyclic polycarboxylic acid ester compound (ROH; R represents the same definition as R in the above formula (a)), a linear alcohol having 3 to 18 carbon atoms, carbon A branched alcohol having 3 to 18 carbon atoms or a cycloalcohol having 5 to 10 carbon atoms may be mentioned. Specifically, linear or branched propanol (including n-propanol, 1-methylethanol, etc.), linear or branched butanol (n-butanol, 1-methylpropanol, 2-methyl) Propanol etc.), linear or branched pentanol (including n-pentanol, 1-methylbutanol, 2-methylbutanol, 3-methylbutanol, etc.), linear or branched hexanol (Including n-hexanol, 1-methylpentanol, 2-methylpentanol, 3-methylpentanol, etc.), linear or branched heptanol (n-heptanol, 1-methylhexanol, 2-methylhexanol) , 3-methylhexanol, 4-methylhexanol, 5-methylhexanol, 2,4-dimethylpentanol, etc. Linear) or branched octanol (including n-octanol, 2-ethylhexanol, 1-methylheptanol, 2-methylheptanol, etc.), linear or branched nonanol (n- Nonanol, 1-methyloctanol, 3,5,5-trimethylhexanol, 1- (2′-methylpropyl) -3-methylbutanol and the like), linear or branched decanol (n-decanol, iso) -Including decanol, etc.), linear or branched undecanol (including n-undecanol, etc.), linear or branched dodecanol (including n-dodecanol, iso-dodecanol, etc.), linear Or branched tridecanol, linear or branched tetradecanol (n-tetradecanol, iso-tetradecanol, etc.) ), Linear or branched pentadecanol, linear or branched hexadecanol (including n-hexadecanol, iso-hexadecanol, etc.), linear or branched Heptadecanol, linear or branched octadecanol (including n-octadecanol, iso-octadecanol, etc.), cyclohexanol, methylcyclohexanol, dimethylcyclohexanol and the like.

  In carrying out the esterification reaction, for example, the alcohol component is used in an amount of 1.0 to 1.5 equivalents, preferably 1.05 to 1.2 equivalents, per 1 equivalent of acid.

  Further, instead of the acid component and the alcohol component, an alicyclic polyvalent carboxylic acid ester compound is obtained by a transesterification reaction using a lower alcohol ester of the acid component and / or an acetic acid ester or propionic acid ester of the alcohol. It is also possible to obtain.

  Examples of esterification catalysts include Lewis acids, alkali metal salts, sulfonic acids, and the like. Specific examples of Lewis acids include aluminum derivatives, tin derivatives, titanium derivatives, and the like. Examples of alkali metal salts include sodium alkoxides. And potassium alkoxides, and examples of the sulfonic acids include p-toluenesulfonic acid, methanesulfonic acid, and sulfuric acid. The amount used is, for example, about 0.1 to 1% by mass with respect to the total amount of the acid component and alcohol component as raw materials.

  Examples of the temperature at the time of esterification include 150 ° C to 230 ° C, and the reaction is usually completed in 3 to 30 hours.

  After completion of the esterification reaction, excess raw materials are distilled off under reduced pressure or vapor pressure, and then the ester compound is purified by a conventional purification method such as adsorption purification treatment such as liquid-liquid extraction, vacuum distillation, activated carbon treatment, etc. be able to.

  In addition, the alicyclic polyvalent carboxylic acid ester compound in the present invention can also be obtained by nuclear hydrogenation of a corresponding aromatic polyvalent carboxylic acid ester compound.

  The content of the alicyclic polyvalent carboxylic acid ester compound according to the present invention is required to be 1% by mass or more on the basis of the total amount of the composition from the viewpoint of improvement in processing efficiency and tool life, preferably 5 It is at least 10% by mass, more preferably at least 10% by mass. Further, the content of the alicyclic polyvalent carboxylic acid ester compound is required to be 50% by mass or less, preferably 45% by mass or less, more preferably 40% by mass or less, based on the total amount of the composition. Preferably it is 35 mass% or less. When the content of the alicyclic polyvalent carboxylic acid ester compound exceeds 50% by mass, the handleability decreases, for example, the stickiness increases. Further, as will be described later, the metalworking oil composition of the present invention may contain an additive, but when the content of the alicyclic polyvalent carboxylic acid ester compound exceeds 50% by mass, the characteristics are improved by the additive. The effect tends to be insufficient.

  The metalworking oil composition of the present invention contains the above-described hydrocarbon oil and alicyclic polyvalent carboxylic acid ester compound, but other conventionally known lubricant oils are used to the extent that their performance is not significantly reduced. The base oil can be used. As other base oils, for example, esters (diesters, triesters, polyol esters, etc.) other than the above alicyclic polycarboxylic acid ester compounds, polyoxyalkylene glycols, polyphenyl ethers, and the like can be used. The content in the case of using these base oils is not particularly limited, but is preferably 65% by mass or less, more preferably 50% by mass or less, and 30% by mass or less based on the total amount of the composition. More preferably, it is more preferably 20% by mass or less, and particularly preferably 10% by mass or less.

  The metalworking oil composition of the present invention preferably contains an oily agent from the viewpoint of further improving the working efficiency and tool life. Examples of the oily agent include (A) alcohol, (B) carboxylic acid, (C) a sulfide of unsaturated carboxylic acid, (D) a compound represented by the following general formula (1), (E) the following general formula (2 ), (F) polyoxyalkylene compounds, (G) esters, (H) polyhydric alcohol hydrocarbyl ethers, (I) amines, and the like.

[In Formula (1), ^{R 1} represents a hydrocarbon group having 1 to 30 carbon atoms, a represents an integer of 1 to 6, b is an integer of 0-5. ]

[In formula (2), ^{R 2} represents a hydrocarbon group having 1 to 30 carbon atoms, c is an integer of 1 to 6, d is an integer of 0-5. ]

  (A) The alcohol may be a monohydric alcohol or a polyhydric alcohol. A monohydric alcohol having 1 to 40 carbon atoms is preferable, higher alcohols having 1 to 25 carbon atoms are more preferable, and alcohols having 8 to 18 carbon atoms are most preferable in terms of obtaining higher processing efficiency and tool life. . These alcohols may be linear or branched, and may be saturated or unsaturated, but are preferably saturated from the viewpoint of anti-stickiness. Specifically, the same thing as the monohydric alcohol and polyhydric alcohol which were illustrated in description of above-mentioned ester can be mentioned.

  (B) The carboxylic acid may be a monobasic acid or a polybasic acid. A monovalent carboxylic acid having 1 to 40 carbon atoms is preferable, higher carboxylic acid having 5 to 25 carbon atoms, and most preferably 5 to 20 carbon atoms from the viewpoint of obtaining higher processing efficiency and tool life. Carboxylic acid. These carboxylic acids may be linear or branched and may be saturated or unsaturated, but are preferably saturated carboxylic acids from the standpoint of stickiness prevention. Specifically, the same thing as the monobasic acid and polybasic acid which were illustrated in description of above-mentioned ester can be mentioned.

  (C) As a sulfide of unsaturated carboxylic acid, the sulfide of unsaturated thing among the carboxylic acids of said (B) can be mentioned, for example. Specific examples include sulfides of oleic acid.

(D) In the compound represented by the general formula (1), examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ include, for example, a linear or branched alkyl group having 1 to 30 carbon atoms, A cycloalkyl group having 5 to 7 carbon atoms, an alkylcycloalkyl group having 6 to 30 carbon atoms, a linear or branched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an alkyl having 7 to 30 carbon atoms Examples include an aryl group and an arylalkyl group having 7 to 30 carbon atoms. In these, it is preferable that it is a C1-C30 linear or branched alkyl group, More preferably, it is a C1-C20 linear or branched alkyl group, More preferably, it is a C1-C10. A linear or branched alkyl group, and most preferably a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a linear or branched propyl group, and a linear or branched butyl group.

  The substitution position of the hydroxyl group is arbitrary, but when it has two or more hydroxyl groups, it is preferably substituted with an adjacent carbon atom. a is preferably an integer of 1 to 3, and more preferably 2. b is preferably an integer of 0 to 3, more preferably 1 or 2. Examples of the compound represented by the general formula (1) include p-tert-butylcatechol.

(E) In the compound represented by the general formula (2), examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ² are represented by R ¹ in the general formula (1). The same thing as the example of a C1-C30 hydrocarbon group can be mentioned, and the example of a preferable thing is also the same. The substitution position of the hydroxyl group is arbitrary, but when it has two or more hydroxyl groups, it is preferably substituted with an adjacent carbon atom. c is preferably an integer of 1 to 3, and more preferably 2. d is preferably an integer of 0 to 3, more preferably 1 or 2. Examples of the compound represented by the general formula (2) include 2,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene.

  (F) As a polyoxyalkylene compound, the compound represented, for example by the following general formula (3) or (4) can be mentioned.

_{^{R 3 O- (R 4 O)}} e -R 5 (3)
[In Formula (3), R ³ and R ⁵ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, R ⁴ represents an alkylene group having 2 to ⁴ carbon atoms, and e represents a number average molecular weight. Represents an integer such that 100 is 3500. ]

^{A - [(R 6 O)} f -R 7] g (4)
Wherein (4), A is hydroxyl represents 2.1-3.5 removing some or all of the hydrogen atoms of the hydroxyl groups of an alcohol having 3 to 10, R ⁶ is an alkylene group having 2 to 4 carbon atoms R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, f represents an integer having a number average molecular weight of 100 to 3500, and g represents the number of hydrogen atoms removed from the hydroxyl group of A. Represents the same number. ]

In the general formula (3), at least one of R ³ and R ⁵ is preferably a hydrogen atom. Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ³ and R ^5, for example, the same as the examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ in the general formula (1) Examples of preferred ones are also the same. Specific examples of the alkylene group having 2 to 4 carbon atoms represented by R ⁴ include an ethylene group, a propylene group (methylethylene group), and a butylene group (ethylethylene group). e is preferably an integer such that the number average molecular weight is 300 to 2,000, and more preferably an integer such that the number average molecular weight is 500 to 1,500.

  Moreover, in the said General formula (4), as a specific example of the polyhydric alcohol which has 3-10 hydroxyl groups which comprise A, glycerin, polyglycerin (2-tetramer of glycerin, for example, diglycerin, triglycerin) , Tetraglycerin), trimethylolalkanes (trimethylolethane, trimethylolpropane, trimethylolbutane) and their 2-tetramers, pentaerythritol, dipentaerythritol, 1,2,4-butanetriol, 1,3, 5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol, idylitol, taritol, dulcitol, allitol Multivalent such as Alcohol; it xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, Mantosu, be mentioned Isomantosu, trehalose, and a saccharide such as sucrose. Among these, glycerin, polyglycerin, trimethylolalkane, and dimer to tetramer thereof, pentaerythritol, dipentaerythritol, sorbitol, or sorbitan are preferable.

Examples of the alkylene group having 2 to 4 carbon atoms represented by R ⁶ may be the same as the examples of the alkylene group having 2 to 4 carbon atoms represented by R ⁴ in the general formula (3) . As examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ⁷ are given the same as examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ in the general formula (1) Examples of preferred ones are the same. At least one of g R ⁷ is preferably a hydrogen atom, more preferably all hydrogen atoms. f is preferably an integer such that the number average molecular weight is 300 to 2,000, more preferably an integer such that the number average molecular weight is 500 to 1,500.

  (G) As ester, the alcohol which comprises this may be monohydric alcohol or polyhydric alcohol, and carboxylic acid may be monobasic acid or polybasic acid.

  Examples of the monohydric alcohol and polyhydric alcohol constituting the ester oily agent may be a monohydric alcohol or a polyhydric alcohol, and the acid constituting the ester oily agent may be a monobasic acid or a polybasic acid. Good.

  As the monohydric alcohol, those having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms are usually used. Such alcohols may be linear or branched, and saturated. Or may be unsaturated. Specific examples of the alcohol having 1 to 24 carbon atoms include methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched pentanol, and linear Linear or branched hexanol, linear or branched heptanol, linear or branched octanol, linear or branched nonanol, linear or branched decanol, linear or branched Undecanol, linear or branched dodecanol, linear or branched tridecanol, linear or branched tetradecanol, linear or branched pentadecanol, linear or branched hexadecane Decanol, linear or branched heptadecanol, linear or branched octadecanol, linear or branched nonadecanol, linear or branched icosa Lumpur, linear or branched Hen'ikosanoru, linear or branched Torikosanoru, such as linear or branched tetracosanol, and mixtures thereof.

  As the polyhydric alcohol, those having 2 to 10 valences, preferably 2 to 6 valences are usually used. Specific examples of the 2 to 10 polyhydric alcohol include, for example, ethylene glycol, diethylene glycol, polyethylene glycol (3 to 15 mer of ethylene glycol), propylene glycol, dipropylene glycol, and polypropylene glycol (3 to 15 of propylene glycol). Monomer), 1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3 -Dihydric alcohols such as propanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, neopentylglycol; glycerin, polyglycerin (glycerin 2- Octamers such as diglycerin, triglyceride Phosphorus, tetraglycerin, etc.), trimethylolalkanes (trimethylolethane, trimethylolpropane, trimethylolbutane, etc.) and their 2- to 8-mer, pentaerythritol and their 2- to 4-mer, 1,2,4- Butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol, etc. Polysaccharides of xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, sugars, and mixtures thereof That.

  Among these polyhydric alcohols, ethylene glycol, diethylene glycol, polyethylene glycol (ethylene glycol 3-10 mer), propylene glycol, dipropylene glycol, polypropylene glycol (propylene glycol 3-10 mer), 1,3- Propanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, glycerin, diglycerin, triglycerin, trimethylolalkane (trimethylolethane, trimethylolpropane, trimethylol Methylol butane and the like, and dimers and tetramers thereof, pentaerythritol, dipentaerythritol, 1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol , 1,2,3,4 butane tetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, divalent to hexavalent polyhydric alcohols and mixtures thereof, such as mannitol and the like are preferable. Even more preferred are ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitan, and mixtures thereof. Among these, neopentyl glycol, trimethylol ethane, trimethylol propane, pentaerythritol, and a mixture thereof are most preferable because higher thermal and oxidation stability can be obtained.

  As described above, the alcohol constituting the ester oily agent may be a monohydric alcohol or a polyhydric alcohol, but it is possible to achieve better processing efficiency and tool life, and a low pour point. Polyhydric alcohols are preferred from the standpoints that products are easier to obtain and handleability in winter and cold regions is improved. Further, when an ester of polyhydric alcohol is used, in the cutting / grinding process, the accuracy of the finished surface of the workpiece is improved and the effect of preventing wear of the tool edge is further increased.

  Of the acids constituting the ester oily agent, as the monobasic acid, a fatty acid having 2 to 24 carbon atoms is usually used. The fatty acid may be linear or branched, and may not be saturated. It may be saturated. Specifically, for example, acetic acid, propionic acid, linear or branched butanoic acid, linear or branched pentanoic acid, linear or branched hexanoic acid, linear or branched heptane Acid, linear or branched octanoic acid, linear or branched nonanoic acid, linear or branched decanoic acid, linear or branched undecanoic acid, linear or branched dodecane Acid, linear or branched tridecanoic acid, linear or branched tetradecanoic acid, linear or branched pentadecanoic acid, linear or branched hexadecanoic acid, linear or branched heptadecane Acid, linear or branched octadecanoic acid, linear or branched hydroxyoctadecanoic acid, linear or branched nonadecanoic acid, linear or branched icosanoic acid, linear or branched Henicosanoic acid, linear or branched Saturated fatty acids such as cosanoic acid, linear or branched tricosanoic acid, linear or branched tetracosanoic acid, acrylic acid, linear or branched butenoic acid, linear or branched pentenoic acid, Linear or branched hexenoic acid, linear or branched heptenoic acid, linear or branched octenoic acid, linear or branched nonenoic acid, linear or branched decenoic acid, Linear or branched undecenoic acid, linear or branched dodecenoic acid, linear or branched tridecenoic acid, linear or branched tetradecenoic acid, linear or branched pentadecenoic acid, Linear or branched hexadecenoic acid, linear or branched heptadecenoic acid, linear or branched octadecenoic acid, linear or branched hydroxyoctadecenoic acid, linear or branched nonadecene Acid, linear or branched Unsaturated fatty acids such as cocenoic acid, linear or branched heicosenoic acid, linear or branched docosenoic acid, linear or branched tricosenoic acid, linear or branched tetracosenoic acid, and the like And the like. Among these, from the viewpoint of improvement in processing efficiency and tool life, and handleability, a saturated fatty acid having 3 to 20 carbon atoms, an unsaturated fatty acid having 3 to 22 carbon atoms, and a mixture thereof are particularly preferable, and those having 4 to 18 carbon atoms. Saturated fatty acids, unsaturated fatty acids having 4 to 18 carbon atoms and mixtures thereof are more preferred, unsaturated fatty acids having 4 to 18 carbon atoms are more preferred, and saturated fatty acids having 4 to 18 carbon atoms are further preferred from the viewpoint of anti-stickiness. preferable.

  Examples of the polybasic acid include dibasic acids having 2 to 16 carbon atoms and trimellitic acid. The dibasic acid having 2 to 16 carbon atoms may be linear or branched, and may be saturated or unsaturated. Specifically, for example, ethanedioic acid, propanedioic acid, linear or branched butanedioic acid, linear or branched pentanedioic acid, linear or branched hexanedioic acid, linear Or branched heptanedioic acid, linear or branched octanedioic acid, linear or branched nonanedioic acid, linear or branched decanedioic acid, linear or branched undecanedioic acid Acid, linear or branched dodecanedioic acid, linear or branched tridecanedioic acid, linear or branched tetradecanedioic acid, linear or branched heptadecanedioic acid, linear or Branched hexadecanedioic acid, linear or branched hexenedioic acid, linear or branched heptenedioic acid, linear or branched octenedioic acid, linear or branched nonenedioic acid , Linear or branched decenedioic acid, linear or branched undecenedioic acid, linear Is branched dodecenedioic acid, linear or branched tridecenedioic acid, linear or branched tetradecenedioic acid, linear or branched heptadecenedioic acid, linear or branched hexadecene diacid Examples thereof include acids and mixtures thereof.

  The combination of an alcohol and an acid in the ester oily agent is arbitrary and not particularly limited. Examples of the ester oily agent that can be used in the present invention include the following esters.

(G-1) Ester of monohydric alcohol and monobasic acid (G-2) Ester of polyhydric alcohol and monobasic acid (G-3) Ester of monohydric alcohol and polybasic acid (G-4) Ester of polyhydric alcohol and polybasic acid (G-5) Monohydric alcohol, mixed ester of polyhydric alcohol and polybasic acid (G-6) Polyhydric alcohol and monobasic acid, polybasic acid (G-7) Monohydric alcohol, mixture of polyhydric alcohol and monobasic acid, polybasic acid

  When a polyhydric alcohol is used as the alcohol component, it may be a complete ester in which all the hydroxyl groups in the polyhydric alcohol are esterified, or a partial ester in which some of the hydroxyl groups are not esterified and remain as hydroxyl groups. Good. Further, when a polybasic acid is used as the carboxylic acid component, it may be a complete ester in which all the carboxyl groups in the polybasic acid are esterified, or a part of the carboxyl group is not esterified and remains as a carboxyl group. It may be a partial ester.

The total number of carbon atoms of the ester oil-based agent is not particularly limited, but from the viewpoint of improving processing efficiency and tool life, an ester having a total carbon number of 7 or more is preferable, an ester of 9 or more is more preferable, and an ester of 11 or more is preferable. Most preferred. Further, from the viewpoint of not increasing the occurrence of stain and corrosion, and compatibility with organic materials, an ester having a total carbon number of 60 or less is preferred, an ester of 45 or less is more preferred, an ester of 26 or less is more preferred, 24 or less esters are more preferred, and 22 or less esters are most preferred.

  (H) As a polyhydric alcohol which comprises the hydrocarbyl ether of a polyhydric alcohol, a 2-10 valence, Preferably a 2-6 valence thing is used. Specific examples of the 2 to 10 polyhydric alcohol include, for example, ethylene glycol, diethylene glycol, polyethylene glycol (3 to 15 mer of ethylene glycol), propylene glycol, dipropylene glycol, and polypropylene glycol (3 to 15 of propylene glycol). Monomer), 1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3 -Dihydric alcohols such as propanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, neopentylglycol; glycerin, polyglycerin (glycerin 2- Octamers such as diglycerin, triglyceride Phosphorus, tetraglycerin, etc.), trimethylolalkanes (trimethylolethane, trimethylolpropane, trimethylolbutane, etc.) and their 2- to 8-mer, pentaerythritol and their 2- to 4-mer, 1,2,4- Butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol, etc. Polysaccharides of xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, sugars, and mixtures thereof That.

  Among these polyhydric alcohols, ethylene glycol, diethylene glycol, polyethylene glycol (ethylene glycol 3-10 mer), propylene glycol, dipropylene glycol, polypropylene glycol (propylene glycol 3-10 mer), 1,3- Propanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, glycerin, diglycerin, triglycerin, trimethylolalkane (trimethylolethane, trimethylolpropane, trimethylol Methylol butane and the like, and dimers and tetramers thereof, pentaerythritol, dipentaerythritol, 1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol , 1,2,3,4 butane tetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, divalent to hexavalent polyhydric alcohols and mixtures thereof, such as mannitol and the like are preferable. Even more preferred are ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitan, and mixtures thereof. Among these, glycerin is most preferable from the viewpoint of improving the processing efficiency and the tool life.

  (H) As the hydrocarbyl ether of the polyhydric alcohol, one obtained by converting a part or all of the hydroxyl groups of the polyhydric alcohol into a hydrocarbyl ether can be used. From the viewpoint of improving processing efficiency and tool life, a product obtained by hydrocarbyl etherifying a part of hydroxyl groups of a polyhydric alcohol (partially etherified product) is preferable. Here, the hydrocarbyl group is an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an alkylcycloalkyl group having 6 to 11 carbon atoms, carbon A hydrocarbon group having 1 to 24 carbon atoms such as an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms, and an arylalkyl group having 7 to 18 carbon atoms is represented.

  Examples of the alkyl group having 1 to 24 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, linear or branched pentyl. Group, linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched decyl group, linear or Branched undecyl group, linear or branched dodecyl group, linear or branched tridecyl group, linear or branched tetradecyl group, linear or branched pentadecyl group, linear or branched hexadecyl group , Linear or branched heptadecyl group, linear or branched octadecyl group, linear or branched nonadecyl group, linear or branched icosyl group, linear or branched heicosyl group, linear or branched Branched docosyl group, linear or branched tri Sill group, such as a straight-chain or branched tetracosyl groups.

  Examples of the alkenyl group having 2 to 24 carbon atoms include a vinyl group, a linear or branched propenyl group, a linear or branched butenyl group, a linear or branched pentenyl group, and a linear or branched hexenyl group. Linear or branched heptenyl group, linear or branched octenyl group, linear or branched nonenyl group, linear or branched decenyl group, linear or branched undecenyl group, linear or branched A branched dodecenyl group, a linear or branched tridecenyl group, a linear or branched tetradecenyl group, a linear or branched pentadecenyl group, a linear or branched hexadecenyl group, a linear or branched heptadecenyl group, Linear or branched octadecenyl group, linear or branched nonadecenyl group, linear or branched icocenyl group, linear or branched henicosenyl group, linear or branched dococenyl group, linear or branched Tricosenyl group, straight chain The like tetracosenyl group branched thereof.

  Examples of the cycloalkyl group having 5 to 7 carbon atoms include cyclpentyl group, cyclohexyl group, and cycloheptyl group. Examples of the alkylcycloalkyl group having 6 to 11 carbon atoms include methylcyclopentyl group, dimethylcyclopentyl group (including all structural isomers), methylethylcyclopentyl group (including all structural isomers), and diethylcyclopentyl group ( Including all structural isomers), methylcyclohexyl group, dimethylcyclohexyl group (including all structural isomers), methylethylcyclohexyl group (including all structural isomers), diethylcyclohexyl group (all structures) Isomers), methylcycloheptyl group, dimethylcycloheptyl group (including all structural isomers), methylethylcycloheptyl group (including all structural isomers), diethylcycloheptyl group (all Including structural isomers).

  Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group. Examples of the alkylaryl group having 7 to 18 carbon atoms include a tolyl group (including all structural isomers), a xylyl group (including all structural isomers), and an ethylphenyl group (including all structural isomers). ), Linear or branched propylphenyl group (including all structural isomers), linear or branched butylphenyl group (including all structural isomers), linear or branched pentylphenyl A group (including all structural isomers), a linear or branched hexylphenyl group (including all structural isomers), a linear or branched heptylphenyl group (including all structural isomers). ), Linear or branched octylphenyl group (including all structural isomers), linear or branched nonylphenyl group (including all structural isomers), linear or branched decylphenyl Group (including all structural isomers), linear or Undecylphenyl branches (including all structural isomers.) (Including all structural isomers.) Linear or branched dodecylphenyl group and the like.

  Examples of the arylalkyl group having 7 to 18 carbon atoms include a benzyl group, a phenylethyl group, a phenylpropyl group (including an isomer of a propyl group), a phenylbutyl group (including an isomer of a butyl group), a phenylpentyl group ( Pentyl group isomers), phenylhexyl group (including hexyl isomers), and the like.

  Among these, from the viewpoint of improvement in machining efficiency and tool life, a linear or branched alkyl group having 2 to 18 carbon atoms and a linear or branched alkenyl group having 2 to 18 carbon atoms are preferable, and the number of carbon atoms 3-12 linear or branched alkyl groups and oleyl groups (residues obtained by removing hydroxyl groups from oleyl alcohol) are more preferred.

  (I) Monoamine is preferably used as the amine. The carbon number of the monoamine is preferably 6 to 24, more preferably 12 to 24. The carbon number here means the total number of carbon atoms contained in the monoamine. When the monoamine has two or more hydrocarbon groups, it represents the total number of carbon atoms.

  As the monoamine used in the present invention, any of a primary monoamine, a secondary monoamine, and a tertiary monoamine can be used, but a primary monoamine is preferable from the viewpoint of improving processing efficiency and tool life. .

  As the hydrocarbon group bonded to the nitrogen atom of the monoamine, any of an alkyl group, alkenyl group, cycloalkyl group, alkylcycloalkyl group, aryl group, alkylaryl group, arylalkyl group, etc. can be used. From the viewpoint of improving efficiency and tool life, an alkyl group or an alkenyl group is preferable. The alkyl group and alkenyl group may be linear or branched, but are preferably linear from the viewpoint of improving processing efficiency and tool life.

  Preferable monoamines used in the present invention include, for example, hexylamine (including all isomers), heptylamine (including all isomers), and octylamine (including all isomers). , Nonylamine (including all isomers), decylamine (including all isomers), undecylamine (including all isomers), dodecylamine (including all isomers), tridecylamine (all Including isomers), tetradecylamine (including all isomers), pentadecylamine (including all isomers), hexadecylamine (including all isomers), heptadecylamine (all isomers) ), Octadecylamine (including all isomers), nonadecylamine (including all isomers), icosylamine (including all isomers), hen Cosylamine (including all isomers), docosylamine (including all isomers), tricosylamine (including all isomers), tetracosylamine (including all isomers), octadecenylamine (all (Including isomers) (including oleylamine and the like) and mixtures of two or more thereof. Among these, from the viewpoint of improvement in machining efficiency and tool life, primary monoamines having 12 to 24 carbon atoms are preferable, primary monoamines having 14 to 20 carbon atoms are more preferable, and primary monoamines having 16 to 18 carbon atoms are preferable. Grade monoamines are more preferred.

  In this invention, only 1 type chosen from the said oil-based agent (A)-(I) may be used, and 2 or more types of mixtures may be used. Among these, it is preferable that it is 1 type, or 2 or more types of mixtures chosen from (B) carboxylic acid and (I) amine from the point of an improvement of work efficiency and tool life.

  The content of the oily agent is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, more preferably 0.05% by mass or more, based on the total amount of the composition, from the viewpoint of improvement in processing efficiency and tool life. Preferably it is 0.1 mass% or more. From the viewpoint of stability, the content of the oily agent is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less, based on the total amount of the composition.

  Moreover, it is preferable that the metalworking oil of the present invention further contains an extreme pressure agent. Preferred extreme pressure agents include sulfur compounds and phosphorus compounds described below.

  The sulfur compound used in the present invention is not particularly limited as long as the properties of the metalworking oil composition are not impaired, but dihydrocarbyl polysulfide, sulfide ester, sulfide mineral oil, zinc dithiophosphate, zinc dithiocarbamate, dithiophosphorus A molybdenum acid compound and molybdenum dithiocarbamate are preferably used.

The dihydrocarbyl polysulfide is a sulfur compound generally called polysulfide or sulfurized olefin, and specifically means a compound represented by the following general formula (5).
_{^{R 8 -S h -R 9 (5}} )
[In Formula (5), R ⁸ and R ⁹ may be the same or different, and each has a linear or branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a carbon number. It represents a 7-20 alkylaryl group or a C7-20 arylalkyl group, and h represents an integer of 2-6, preferably 2-5. ]

As R ⁸ and R ⁹ in the general formula (5), specifically, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, straight chain or Branched pentyl group, linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched decyl group, linear or branched Undecyl group, linear or branched dodecyl group, linear or branched tridecyl group, linear or branched tetradecyl group, linear or branched pentadecyl group, linear or branched hexadecyl group, linear or branched heptadecyl group A linear or branched alkyl group such as a linear or branched octadecyl group, a linear or branched nonadecyl group, a linear or branched icosyl group; an aryl group such as a phenyl group or a naphthyl group; a tolyl group ( Includes all structural isomers , Ethylphenyl group (including all structural isomers), linear or branched propylphenyl group (including all structural isomers), linear or branched butylphenyl group (including all structural isomers), Linear or branched pentylphenyl group (including all structural isomers), linear or branched hexylphenyl group (including all structural isomers), linear or branched heptylphenyl group (all structural isomers) Straight chain or branched octylphenyl group (including all structural isomers), straight chain or branched nonylphenyl group (including all structural isomers), straight chain or branched decylphenyl group (all ), Linear or branched undecylphenyl group (including all structural isomers), linear or branched dodecylphenyl group (including all structural isomers), xylyl group (all Including structural isomers), ethyl Methylphenyl group (including all structural isomers), diethylphenyl group (including all structural isomers), di (straight or branched) propylphenyl group (including all structural isomers), di (direct Chain or branched) butylphenyl group (including all structural isomers), methylnaphthyl group (including all structural isomers), ethylnaphthyl group (including all structural isomers), linear or branched propyl Naphthyl group (including all structural isomers), linear or branched butyl naphthyl group (including all structural isomers), dimethylnaphthyl group (including all structural isomers), ethylmethylnaphthyl group (all Including structural isomers), diethyl naphthyl group (including all structural isomers), di (linear or branched) propyl naphthyl group (including all structural isomers), di (straight or branched) butyl Naphthyl group (all Alkylaryl groups such as isomers); arylalkyl groups such as benzyl, phenylethyl groups (including all isomers), and phenylpropyl groups (including all isomers); .

Among them, R ⁸ and R ⁹ in the general formula (5), propylene, 1-butene or an alkyl group has been 3 to 18 carbon atoms derived from isobutylene, or an aryl group having a carbon number of 6-8, alkyl An aryl group or an arylalkyl group is preferable. Examples of these groups include isopropyl group, branched hexyl group derived from propylene dimer (including all branched isomers), and propylene trimer. Branched nonyl groups derived from the body (including all branched isomers), branched dodecyl groups derived from the propylene tetramer (including all branched isomers), 5 quantities of propylene Branched pentadecyl groups derived from the body (including all branched isomers), branched octadecyl groups derived from the propylene hexamer (including all branched isomers), sec Branched octyl group derived from butyl group, tert-butyl group, 1-butene dimer (including all branched isomers), branched octyl group derived from isobutylene dimer (all ), Branched dodecyl groups derived from 1-butene trimer (including all branched isomers), branched dodecyl groups derived from isobutylene trimer (Including all branched isomers), branched hexadecyl group derived from 1-butene tetramer (including all branched isomers), branched derived from isobutylene tetramer Alkyl groups such as hexadecyl group (including all branched isomers); phenyl group, tolyl group (including all structural isomers), ethylphenyl group (including all structural isomers), xylyl group (all (Including structural isomers) Groups; arylalkyl groups such as benzyl group and phenylethyl group (including all isomers).

Furthermore, R ⁸ and R ⁹ in the general formula (5) are each independently a branched alkyl group having 3 to 18 carbon atoms derived from ethylene or propylene, from the viewpoint of improving the processing efficiency and tool life. It is more preferable that it is a branched alkyl group having 6 to 15 carbon atoms derived from ethylene or propylene.

Specific examples of the sulfurized ester include animal and vegetable fats and oils such as beef tallow, pork tallow, fish and fat, rapeseed oil and soybean oil; ) And various alcohols, and unsaturated fatty acid esters obtained by reacting them with alcohols; and those obtained by sulfiding a mixture thereof by any method.

  Sulfided mineral oil refers to one obtained by dissolving elemental sulfur in mineral oil. Here, the mineral oil used in the sulfide mineral oil according to the present invention is not particularly limited, and specifically, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and vacuum distillation is solvent desorbed and solvent extracted. , Hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, washing with sulfuric acid, paraffinic mineral oil, naphthenic mineral oil, etc. purified by appropriately combining purification treatments such as clay treatment. In addition, as the elemental sulfur, any form such as a lump, powder, molten liquid, etc. may be used, but when powdered or molten liquid elemental sulfur is used, it is efficiently dissolved in the base oil. Is preferable. In addition, molten liquid elemental sulfur has the advantage that the melting operation can be performed in a very short time because the liquids are mixed together, but it must be handled above the melting point of elemental sulfur, heating equipment, etc. It is not always easy to handle because it requires special equipment and is handled in a high temperature atmosphere. On the other hand, powdery simple sulfur is particularly preferable because it is inexpensive and easy to handle, and the time required for dissolution is sufficiently short. Moreover, although there is no restriction | limiting in particular in the sulfur content in the sulfide mineral oil concerning this invention, Preferably it is 0.05-1.0 mass% normally on the basis of the sulfide mineral oil whole quantity, More preferably, it is 0.1-0. 5% by mass.

  The zinc dithiophosphate compound, the zinc dithiocarbamate compound, the molybdenum dithiophosphate and the molybdenum dithiocarbamate mean compounds represented by the following general formulas (6) to (9), respectively.

[In the formulas (6) to (9), R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ may be the same or different and each represents a hydrocarbon group having 1 or more carbon atoms, and X ¹ and X ² each represent an oxygen atom or a sulfur atom. ]

Here, R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ Specific examples of the hydrocarbon group represented by: methyl group, ethyl group, propyl group (including all branched isomers), butyl group (including all branched isomers), pentyl group (including Including all branched isomers), hexyl group (including all branched isomers), heptyl group (including all branched isomers), octyl group (including all branched isomers), nonyl Groups (including all branched isomers), decyl groups (including all branched isomer pairs), undecyl groups (including all branched isomer pairs), dodecyl groups (including all branched isomer pairs) , Tridecyl group (including all branched pairs), tetradec Groups (including all branched isomer pairs), pentadecyl groups (including all branched isomer pairs), hexadecyl groups (including all branched isomer pairs), heptadecyl groups (including all branched isomer pairs) , Octadecyl group (including all branched isomer pairs), nonadecyl group (including all branched isomer pairs), icosyl group (including all branched isomer pairs), heicosyl group (including all branched isomer pairs) Alkyl groups such as docosyl groups (including all branched isomer pairs), tricosyl groups (including all branched isomer pairs), tetracosyl groups (including all branched isomer pairs); cyclopentyl groups, cyclohexyl Group, cycloalkyl group such as cycloheptyl group; methylcyclopentyl group (including all substituted isomers), ethylcyclopentyl group (including all substituted isomers), dimethyl Clopentyl group (including all substituted isomers), propylcyclopentyl group (including all branched isomers, including substituted isomers), methylethylcyclopentyl group (including all substituted isomers), trimethylcyclopentyl group (including all substituted isomers) Substituted isomers), butylcyclopentyl group (all branched isomers, including substituted isomers), methylpropylcyclopentyl group (including all branched isomers, substituted isomers), diethylcyclopentyl group (all Substituted isomers), dimethylethylcyclopentyl group (including all substituted isomers), methylcyclohexyl group (including all substituted isomers), ethylcyclohexyl group (including all substituted isomers), dimethylcyclohexyl group (Including all substituted isomers), propylcyclohexyl groups (all Branched isomers, including substituted isomers, methylethylcyclohexyl group (including all substituted isomers), trimethylcyclohexyl group (including all substituted isomers), butylcyclohexyl group (all branched isomers, Substituted isomers), methylpropylcyclohexyl group (including all branched isomers, including substituted isomers), diethylcyclohexyl group (including all substituted isomers), dimethylethylcyclohexyl group (including all substituted isomers) ), Methylcycloheptyl group (including all substituted isomers), ethylcycloheptyl group (including all substituted isomers), dimethylcycloheptyl group (including all substituted isomers), propylcycloheptyl group (including All branched isomers, including substituted isomers), methylethylcycloheptyl group (all substituted isomers) ), Trimethylcycloheptyl group (including all substituted isomers), butylcycloheptyl group (including all branched isomers, including substituted isomers), methylpropylcycloheptyl group (including all branched isomers), Substituted isomers), diethylcycloheptyl group (including all substituted isomers), dimethylethylcycloheptyl group (including all substituted isomers) and other alkyl cycloalkyl groups; phenyl group, naphthyl group and other aryls Group; tolyl group (including all substituted isomers), xylyl group (including all substituted isomers), ethylphenyl group (including all substituted isomers), propylphenyl group (all branched isomers, Substituted isomers), methylethylphenyl group (including all substituted isomers), trimethylphenyl group (including all substituted isomers) ), Butylphenyl group (including all branched and substituted isomers), methylpropylphenyl group (including all branched and substituted isomers), and diethylphenyl group (including all substituted isomers) Dimethylethylphenyl group (including all substituted isomers), pentylphenyl group (including all branched isomers, including substituted isomers), hexylphenyl group (including all branched isomers, substituted isomers) ), Heptylphenyl group (including all branched isomers, substituted isomers), octylphenyl group (including all branched isomers, substituted isomers), nonylphenyl group (all branched isomers, Substituted isomers), decylphenyl group (including all branched isomers, including substituted isomers), undecylphenyl group (including all branched isomers, including substituted isomers), dodecylphenyl Group (including all branched isomers, substituted isomers), tridecylphenyl group (including all branched isomers, substituted isomers), tetradecylphenyl group (all branched isomers, substituted isomers) ), Pentadecylphenyl group (including all branched and substituted isomers), hexadecylphenyl group (including all branched and substituted isomers), heptadecylphenyl group (including all branched isomers) Alkylaryl groups such as branched isomers, including substituted isomers, octadecylphenyl groups (including all branched isomers and substituted isomers); benzyl groups, phenethyl groups, phenylpropyl groups (all branched isomers) And arylalkyl groups such as phenylbutyl group (including all branched isomers).

  In the present invention, among the above sulfur compounds, it is preferable to use at least one selected from the group consisting of dihydrocarbyl polysulfide and sulfurized ester because the effect of improving the machining efficiency and tool life can be obtained at a higher level.

  Specific examples of phosphorus compounds used as extreme pressure agents in the present invention include phosphoric acid esters, acidic phosphoric acid esters, amine salts of acidic phosphoric acid esters, chlorinated phosphoric acid esters, phosphorous acid esters, and phosphors. Examples include thionate and metal salts of phosphorus compounds represented by the following general formula (10) or (11). Examples of these phosphorus compounds include esters of phosphoric acid, phosphorous acid or thiophosphoric acid and alkanols, polyether type alcohols, or derivatives thereof.

[In Formula (10), X ³ , X ⁴ and X ⁵ may be the same or different and each represents an oxygen atom or a sulfur atom, and at least two of X ³ , X ⁴ or X ⁵ are oxygen atoms; , R ²⁶ , R ²⁷ and R ²⁸ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. ]

[In formula (11), X ⁶ , X ⁷ , X ⁸ and X ⁹ may be the same or different and each represents an oxygen atom or a sulfur atom, and at least 3 of X ⁶ , X ⁷ , X ⁸ or X ⁹ One is an oxygen atom, and R ²⁹ , R ³⁰ and R ³¹ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. ]

  More specifically, the phosphate ester includes tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, tridecyl phosphate, triundecyl phosphate, tridodecyl phosphate, tritridecyl Phosphate, tritetradecyl phosphate, tripentadecyl phosphate, trihexadecyl phosphate, triheptadecyl phosphate, trioctadecyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xyl Examples include lenyl diphenyl phosphate.

  Examples of acidic phosphate esters include monobutyl acid phosphate, monopentyl acid phosphate, monohexyl acid phosphate, monoheptyl acid phosphate, monooctyl acid phosphate, monononyl acid phosphate, monodecyl acid phosphate, monoundecyl acid phosphate, monododecyl Acid phosphate, monotridecyl acid phosphate, monotetradecyl acid phosphate, monopentadecyl acid phosphate, monohexadecyl acid phosphate, monoheptadecyl acid phosphate, monooctadecyl acid phosphate, monooleyl acid phosphate, dibutyl acid phosphate, dipentyl acid , Dihexyl reed Dophosphate, diheptyl acid phosphate, dioctyl acid phosphate, dinonyl acid phosphate, didecyl acid phosphate, diundecyl acid phosphate, didodecyl acid phosphate, ditridecyl acid phosphate, ditetradecyl acid phosphate, dipentadecyl acid, dipentadecyl acid Examples include hexadecyl acid phosphate, diheptadecyl acid phosphate, dioctadecyl acid phosphate, and dioleyl acid phosphate.

  Examples of the amine salt of acidic phosphate ester include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, Examples thereof include salts with amines such as dipentylamine, dihexylamine, diheptylamine, dioctylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine and trioctylamine.

  Examples of the chlorinated phosphate ester include tris-dichloropropyl phosphate, tris-chloroethyl phosphate, tris-chlorophenyl phosphate, and polyoxyalkylene bis [di (chloroalkyl)] phosphate.

  As phosphites, dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, dioctyl phosphite, dinonyl phosphite, didecyl phosphite, diundecyl phosphite, didodecyl phosphite, dioleyl Phosphite, diphenyl phosphite, dicresyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, triundecyl phosphite Phyto, tridodecyl phosphite, trioleyl phosphite, triphenyl phosphite, tricresyl phosphite and the like can be mentioned.

  The phosphorothioates include tributyl phosphorothioate, tripentyl phosphorothioate, trihexyl phosphorothionate, triheptyl phosphorothionate, trioctyl phosphorothionate, trinonyl phosphorothionate, tridecyl Phosphorothioate, triundecyl phosphorothionate, tridodecyl phosphorothioate, tritridecyl phosphorothioate, tritetradecyl phosphorothioate, tripentadecyl phosphorothionate, trihexadecyl phosphorothionate , Triheptadecyl phosphorothioate, trioctadecyl phosphorothioate, trioleyl phosphorothioate, triphenyl phosphorothioate, tri Resyl phosphorothioate, trixylenyl phosphorothioate, cresyl diphenyl phosphorothioate, xylenyl diphenyl phosphorothioate, tris (n-propylphenyl) phosphorothionate, tris (isopropylphenyl) phos Phosphorothionate, tris (n-butylphenyl) phosphothionate, tris (isobutylphenyl) phosphothionate, tris (s-butylphenyl) phosphothionate, tris (t-butylphenyl) phosphothionate, etc. Is mentioned.

Moreover, regarding the metal salt of the phosphorus compound represented by the general formula (10) or (11), the hydrocarbon group having 1 to 30 carbon atoms represented by R ^{26 to} R ³¹ in the formula is specifically Includes an alkyl group, a cycloalkyl group, an alkenyl group, an alkylcycloalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, and the like.

  Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group. Group, hexadecyl group, heptadecyl group, octadecyl group and other alkyl groups (these alkyl groups may be linear or branched).

  As said cycloalkyl group, C5-C7 cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, can be mentioned, for example. Examples of the alkylcycloalkyl group include a methylcyclopentyl group, a dimethylcyclopentyl group, a methylethylcyclopentyl group, a diethylcyclopentyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylethylcyclohexyl group, a diethylcyclohexyl group, a methylcycloheptyl group, Examples thereof include an alkylcycloalkyl group having 6 to 11 carbon atoms such as a dimethylcycloheptyl group, a methylethylcycloheptyl group, and a diethylcycloheptyl group (the substitution position of the alkyl group with the cycloalkyl group is also arbitrary).

  Examples of the alkenyl group include butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, An alkenyl group such as an octadecenyl group (these alkenyl groups may be linear or branched, and the position of the double bond is also optional).

  As said aryl group, aryl groups, such as a phenyl group and a naphthyl group, can be mentioned, for example. Examples of the alkylaryl group include tolyl group, xylyl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, and decylphenyl. Group, an alkylaryl group having 7 to 18 carbon atoms such as undecylphenyl group and dodecylphenyl group (the alkyl group may be linear or branched, and the substitution position on the aryl group is arbitrary). .

  Examples of the arylalkyl group include arylalkyl groups having 7 to 12 carbon atoms such as benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, and phenylhexyl group. It may be branched).

The hydrocarbon group having 1 to 30 carbon atoms represented by R ^{26 to} R ³¹ is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 24 carbon atoms, more preferably 3 to 3 carbon atoms. An alkyl group having 18 carbon atoms, more preferably an alkyl group having 4 to 12 carbon atoms.

R ²⁶ , R ²⁷ and R ²⁸ may be the same or different, and each represents a hydrogen atom or the above hydrocarbon group, and among R ²⁶ , R ²⁷ and R ²⁸ , 1 to 3 are the above hydrocarbon groups. It is preferable that 1 to 2 is the above hydrocarbon group, and more preferably 2 is the above hydrocarbon group.

R ²⁹ , R ³⁰ and R ³¹ may be the same or different and each represents a hydrogen atom or the above hydrocarbon group. Among R ²⁹ , R ³⁰ and R ³¹ , 1 to 3 are the above hydrocarbons. It is preferably a group, 1 to 2 are more preferably the hydrocarbon group, and 2 are more preferably the hydrocarbon group.

In the general formula (10) phosphorus compounds represented by, at least two of X ³ to X ⁵ is required to be an oxygen atom, that all X ³ to X ⁵ is an oxygen atom preferable.

Moreover, in the phosphorus compound represented by the general formula (11), it is necessary that at least three of X ^{6 to} X ⁹ are oxygen atoms. BR> K is necessary, but all of X ^{6 to} X ⁹ are An oxygen atom is preferred.

  Examples of the phosphorus compound represented by the general formula (10) include phosphorous acid and monothiophosphorous acid; phosphorous acid monoester having one hydrocarbon group having 1 to 30 carbon atoms and monothiophosphorous acid mono Ester; Phosphorous acid diester having two hydrocarbon groups having 1 to 30 carbon atoms, monothiophosphorous acid diester; Phosphorous acid triester having three hydrocarbon groups having 1 to 30 carbon atoms, monothiophosphorous acid Acid triesters; and mixtures thereof. Among these, phosphorous acid monoester and phosphorous acid diester are preferable, and phosphorous acid diester is more preferable.

  Examples of the phosphorus compound represented by the general formula (11) include phosphoric acid and monothiophosphoric acid; phosphoric acid monoester and monothiophosphoric acid monoester having one hydrocarbon group having 1 to 30 carbon atoms; And phosphoric acid diesters and monothiophosphoric acid diesters having two hydrocarbon groups having 1 to 30 carbon atoms; phosphoric acid triesters and monothiophosphoric acid triesters having three hydrocarbon groups having 1 to 30 carbon atoms; and mixtures thereof. It is done. Among these, phosphoric acid monoester and phosphoric acid diester are preferable, and phosphoric acid diester is more preferable.

  Examples of the metal salt of the phosphorus compound represented by the general formula (10) or (11) include a salt obtained by neutralizing part or all of the acidic hydrogen of the phosphorus compound with a metal base. Examples of such metal bases include metal oxides, metal hydroxides, metal carbonates, metal chlorides and the like. Specific examples of the metal include alkali metals such as lithium, sodium, potassium, cesium, and calcium. And alkaline earth metals such as magnesium and barium, and heavy metals such as zinc, copper, iron, lead, nickel, silver, and manganese. Among these, alkaline earth metals such as calcium and magnesium and zinc are preferable.

  The metal salt of the phosphorus compound has a different structure depending on the valence of the metal and the number of OH groups or SH groups of the phosphorus compound. Therefore, the structure is not limited at all. For example, 1 mol of zinc oxide and phosphoric acid diester ( When 2 mol of 1 OH group is reacted, it is considered that a compound having a structure represented by the following formula (12) is obtained as a main component, but it is also considered that polymerized molecules exist.

  In addition, for example, when 1 mol of zinc oxide and 1 mol of phosphoric acid monoester (two OH groups) are reacted, a compound having a structure represented by the following formula (13) is considered to be obtained as a main component. Polymerized molecules are also thought to exist.

  A mixture of two or more of these can also be used.

  In the present invention, among the above phosphorus compounds, higher processing efficiency and tool life improvement effect can be obtained, and therefore, phosphate esters, acidic phosphate esters, and amine salts of acidic phosphate esters are preferable.

  Further, as described later, the metalworking oil composition of the present invention is applicable to uses other than metalworking, but the metalworking oil composition of the present invention is used as a sliding surface oil for machine tools. It is preferable to contain acidic phosphate ester and amine salt of acidic phosphate ester. Moreover, when using the metalworking oil composition of this invention as a hydraulic fluid, it is preferable to contain phosphate ester. Furthermore, when used as a dual-use oil for sliding surface oil and hydraulic fluid, use at least one selected from acidic phosphate esters and amine salts of acidic phosphate esters in combination with phosphate esters. Is preferred.

  The metalworking oil composition of the present invention may contain only one of a sulfur compound and a phosphorus compound, or may contain both a sulfur compound and a phosphorus compound. From the point that the effect of improving the machining efficiency and the tool life is further enhanced, it preferably contains a phosphorus compound, or both a sulfur compound and a phosphorus compound, and more preferably contains both a sulfur compound and a phosphorus compound.

  Although the content of the extreme pressure agent is arbitrary, it is preferably 0.005% by mass or more and 0.01% by mass or more based on the total amount of the composition from the viewpoint of improving the processing efficiency and tool life. Is more preferable, and it is still more preferable that it is 0.05 mass% or more. From the viewpoint of preventing abnormal wear, the content of the extreme pressure agent is preferably 25% by mass or less, more preferably 20% by mass or less, and more preferably 15% by mass or less, based on the total amount of the composition. Even more preferably, it is even more preferably 10% by mass or less, and most preferably 7% by mass or less.

  In the present invention, only one of the above-mentioned oily agent or extreme pressure agent may be used. However, the oily agent and the extreme pressure agent are used in combination from the viewpoint that higher processing efficiency and an improvement effect of the tool life can be achieved. Is preferred.

  Moreover, in the metal working oil composition of this invention, it is preferable to contain organic acid salt from the point from which the more outstanding processing efficiency and tool life are obtained. As the organic acid salt, sulfonate, phenate, salicylate, and a mixture thereof are preferably used. The positive components of these organic acid salts include alkali metals such as sodium and potassium; alkaline earth metals such as magnesium, calcium and barium; ammonia and alkylamines having 1 to 3 carbon atoms (monomethylamine, dimethyl). Amines, trimethylamines, monoethylamines, diethylamines, triethylamines, monopropylamines, dipropylamines, tripropylamines, etc.), alkanolamines having an alkanol group having 1 to 3 carbon atoms (monomethanolamine, dimethanolamine, trimethanolamine, Monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine etc.) such as amine, zinc, etc. But an alkali metal or alkaline earth metals are preferred, calcium is particularly preferred. When the positive component of the organic acid salt is an alkali metal or alkaline earth metal, higher lubricity tends to be obtained.

  The total base number of the organic acid salt is preferably 50 to 500 mgKOH / g, more preferably 100 to 450 mgKOH / g. When the total base number of the organic acid salt is less than 100 mgKOH / g, the lubricity improving effect due to the addition of the organic acid salt tends to be insufficient. On the other hand, the organic acid salt having a total base number exceeding 500 mgKOH / g is Usually, since manufacture is very difficult and acquisition is difficult, it is unpreferable respectively. The total base number referred to here is JIS K 2501 “Petroleum products and lubricants—Test method for neutralization number”. The total base number [mgKOH / g] by the perchloric acid method measured according to the above.

  Further, the content of the organic acid salt is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% by mass, and further preferably 1 to 20% by mass based on the total amount of the composition. . When the content of the organic acid salt is less than the lower limit value, the effect of improving the processing efficiency and tool life due to the addition of the organic acid salt tends to be insufficient. On the other hand, when the content exceeds the upper limit value, the metal working oil composition There is a tendency that precipitates are likely to be produced due to a decrease in the stability of.

  As the sulfonate, one produced by any method can be used. For example, alkali metal salts, alkaline earth metal salts, amine salts and mixtures of alkyl aromatic sulfonic acids obtained by sulfonating alkyl aromatic compounds having a molecular weight of 100 to 1500, preferably 200 to 700 are used. it can. As the alkyl aromatic sulfonic acid here, generally, a sulfonated alkyl aromatic compound of a lubricating oil fraction of mineral oil, a petroleum sulfonic acid such as so-called mahogany acid, which is by-produced during white oil production, and a detergent Alkylbenzene having a linear or branched alkyl group obtained by by-production from a raw material alkylbenzene production plant or alkylating polyolefin to benzene, or alkylnaphthalene such as dinonylnaphthalene And synthetic sulfonic acids such as those obtained by sulphonation of sulphonate. In addition, the above alkyl aromatic sulfonic acid and an alkali metal base (such as an alkali metal oxide or hydroxide), an alkaline earth metal base (such as an alkaline earth metal oxide or hydroxide), or the above-mentioned So-called neutral (normal salt) sulfonates obtained by reacting with amines (ammonia, alkylamines, alkanolamines, etc.); neutral (normal salt) sulfonates, excess alkali metal bases, alkaline earth metal bases Or so-called basic sulfonates obtained by heating an amine in the presence of water; reacting a neutral (normal salt) sulfonate with an alkali metal base, an alkaline earth metal base or an amine in the presence of carbon dioxide. So called carbonate overbased (superbasic) sulfonates; neutral (normal salt) sulfonates with alkali React with genus bases, alkaline earth metal bases or amines and boric acid compounds such as boric acid or boric anhydride, or carbonate overbased (superbasic) sulfonates with boric acid or boric anhydride And so-called borate overbased (superbasic) sulfonates produced by reacting boric acid compounds; and mixtures thereof.

  Further, as the phenate, specifically, in the presence or absence of elemental sulfur, an alkylphenol having 1 to 2 alkyl groups having 4 to 20 carbon atoms and an alkali metal base (alkali metal oxide or Hydroxides), alkaline earth metal bases (alkaline earth metal oxides, hydroxides, etc.) or neutrals obtained by reacting with the amines mentioned above (ammonia, alkylamines, alkanolamines, etc.). Phenates; neutral phenates and excess alkali metal bases, alkaline earth metal bases or amines obtained by heating in the presence of water, so-called basic phenates; neutral phenates in the presence of carbon dioxide So-called carbonate overbased (superbase) obtained by reacting with metal bases, alkaline earth metal bases or amines ) Phenates; neutral phenates are reacted with alkali metal bases, alkaline earth metal bases or amines and boric acid compounds such as boric acid or boric anhydride, or carbonate overbased (superbasic) phenates And so-called borate overbased (superbasic) phenates produced by reacting boric acid compounds such as boric acid or boric anhydride; and mixtures thereof.

  Further, as the salicylate, specifically, an alkyl salicylic acid having 1 to 2 alkyl groups having 4 to 20 carbon atoms and an alkali metal base (alkali metal oxide) in the presence or absence of elemental sulfur. And hydroxides), alkaline earth metal bases (such as alkaline earth metal oxides and hydroxides) or the above-described amines (such as ammonia, alkylamines and alkanolamines). So-called basic salicylate obtained by heating neutral salicylate and excess alkali metal base, alkaline earth metal base or amine in the presence of water; neutral salicylate in the presence of carbon dioxide gas So-called carbonate overbases obtained by reacting with alkali metal bases, alkaline earth metal bases or amines (Superbasic) salicylates; neutral salicylates react with alkali metal bases, alkaline earth metal bases or amines and boric acid compounds such as boric acid or boric anhydride, or carbonate overbased (superbases) A so-called borate overbased (superbasic) salicylate produced by reacting a metal salicylate with a boric acid compound such as boric acid or anhydrous boric acid; and a mixture thereof.

  In the present invention, the organic acid salt may be used alone, or the organic acid salt and other additives may be used in combination. From the point that machining efficiency and tool life are further improved, it is preferable to use an organic acid salt in combination with the above extreme pressure agent, and it is particularly preferable to use a combination of three types of sulfur compound, phosphorus compound and organic acid salt. .

  Moreover, it is preferable that the metalworking oil composition of the present invention further contains an antioxidant. By adding an antioxidant, it is possible to prevent stickiness due to alteration of the constituent components, and to improve thermal and oxidation stability.

  Antioxidants that can be used include phenolic antioxidants, amine-based antioxidants, zinc dithiophosphate antioxidants, and those used as food additives.

  As the phenolic antioxidant, any phenolic compound used as an antioxidant for lubricating oil can be used, and is not particularly limited. For example, the following general formulas (14) and (15) are used. One type or two or more types of alkylphenol compounds selected from the compounds represented by formula (1) are preferred.

[In the formula (14), R ³² represents an alkyl group having 1 to 4 carbon atoms, R ³³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ³⁴ represents a hydrogen atom, and has 1 to 4 carbon atoms. An alkyl group, a group represented by the following general formula (i) or (ii) is shown. ]

(In the general formula (i), R ³⁵ represents an alkylene group having 1 to 6 carbon atoms, and R ³⁶ represents an alkyl group or alkenyl group having 1 to 24 carbon atoms.)

(In the general formula (ii), R ³⁷ represents an alkylene group having 1 to 6 carbon atoms, R ³⁸ represents an alkyl group having 1 to 4 carbon atoms, and R ³⁹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. And k represents 0 or 1.)

[In General Formula (15), R ⁴⁰ and R ⁴² may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms; R ⁴¹ and R ⁴³ may be the same or different; Represents an atom or an alkyl group having 1 to 4 carbon atoms, R ⁴⁴ and R ⁴⁵ may be the same or different, each represents an alkylene group having 1 to 6 carbon atoms, and A represents an alkylene group having 1 to 18 carbon atoms or The group represented by the following general formula (iii) is shown. ]

-R ⁴⁶ -S-R ^47- (iii)
(In the general formula (iii), R ⁴⁶ and R ⁴⁷ may be the same or different and each represents an alkylene group having 1 to 6 carbon atoms)

  As the amine-based antioxidant used in the present invention, any amine-based compound used as an antioxidant for lubricating oil can be used, and is not particularly limited. For example, the following general formula ( 16) One or two selected from phenyl-α-naphthylamine or Np-alkylphenyl-α-naphthylamine represented by 16) and p, p′-dialkyldiphenylamine represented by the following general formula (17) More than one type of aromatic amine is preferred.

[In the formula (16), R ⁴⁸ represents a hydrogen atom or an alkyl group. ]

[In formula (17), R ⁴⁹ and R ⁵⁰ may be the same or different and each represents an alkyl group. ]

  Specific examples of the amine-based antioxidant include 4-butyl-4'-octyldiphenylamine, phenyl-α-naphthylamine, octylphenyl-α-naphthylamine, dodecylphenyl-α-naphthylamine, and mixtures thereof.

  Specific examples of the zinc dithiophosphate antioxidant used in the present invention include zinc dithiophosphate represented by the following general formula (18).

[In formula (18), R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ may be the same or different and each represents a hydrocarbon group. ]

  Further, an antioxidant used as a food additive can also be used, and partially overlaps with the above-described phenolic antioxidant. For example, for example, 2,6-di-tert-butyl-p-cresol (DBPC), 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-bis (2,6-di-tert-butylphenol), 4,4′-thiobis (6-tert) -Butyl-o-cresol), ascorbic acid (vitamin C), fatty acid ester of ascorbic acid, tocopherol (vitamin E), 3,5-di-tert-butyl-4-hydroxyanisole, 2-tert-butyl-4- Hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, 1,2-dihydro-6-ethoxy-2,2,4-trimethylquinoline (ethoxyquin), 2- (1 , 1-dimethyl) -1,4-benzenediol (TBHQ) and 2,4,5-trihydroxybutyrophenone (THBP).

  Among these antioxidants, those used as phenolic antioxidants, amine antioxidants, and food additives are preferred. Furthermore, when importance is attached to biodegradability, what is used as the said food additive is more preferable, and among them, ascorbic acid (vitamin C), fatty acid ester of ascorbic acid, tocopherol (vitamin E), 2,6- Di-tert-butyl-p-cresol (DBPC), 3,5-di-tert-butyl-4-hydroxyanisole, 2-tert-butyl-4-hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, 1,2-dihydro-6-ethoxy-2,2,4-trimethylquinoline (ethoxyquin), 2- (1,1-dimethyl) -1,4-benzenediol (TBHQ), or 2,4,5-tri Hydroxybutyrophenone (THBP) is preferred, ascorbic acid (vitamin C), fatty acid ester of ascorbic acid, tocopherol (Vitamin E), 2,6-di-tert-butyl-p-cresol (DBPC), or 3,5-di-tert-butyl-4-hydroxyanisole is more preferred.

  The content of the antioxidant is not particularly limited, but in order to maintain good heat / oxidation stability, the content is preferably 0.01% by mass or more based on the total amount of the composition, more preferably 0.05. % By mass or more, most preferably 0.1% by mass or more. On the other hand, since the effect cannot be expected even if it is added more, the content is preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably 3% by mass or less.

  Moreover, the metalworking oil composition of the present invention may contain conventionally known additives other than those described above. Examples of such additives include extreme pressure agents other than the above-described phosphorus compounds and sulfur compounds (including chlorine extreme pressure agents); wetting agents such as diethylene glycol monoalkyl ether; acrylic polymers, paraffin wax, microwax, slack wax Film forming agents such as polyolefin waxes; water displacement agents such as fatty acid amine salts; solid lubricants such as graphite, graphite fluoride, molybdenum disulfide, boron nitride, polyethylene powder; amines, alkanolamines, amides, carboxylic acids, carboxylic acids Corrosion inhibitors such as acid salts, sulfonates, phosphoric acid, phosphates, partial esters of polyhydric alcohols; metal deactivators such as benzotriazoles and thiadiazoles; antifoams such as methylsilicones, fluorosilicones, and polyacrylates Agents: alkenyl succinimide, benzyl amine Emissions, ashless dispersants such as polyalkenyl amines polyaminoamide; and the like. The content when these known additives are used in combination is not particularly limited, but is added in such an amount that the total content of these known additives is 0.1 to 10% by mass based on the total amount of the composition. It is common.

  In addition, although the metalworking oil composition of the present invention may contain a chlorine-based additive such as a chlorine-based extreme pressure agent as described above, from the viewpoint of improving safety and reducing the burden on the environment, It is preferable that no chlorine-based additive is contained. The chlorine concentration is preferably 1000 ppm by mass or less, more preferably 500 ppm by mass or less, still more preferably 200 ppm by mass or less, and 100 ppm by mass or less, based on the total amount of the composition. It is particularly preferred.

Although the kinematic viscosity of the metalworking oil composition of the present invention is not particularly limited, the upper limit value of the kinematic viscosity at 40 ° C. is preferably 200 mm ² / s, more preferably, from the viewpoint of easy supply to the processed part. 100 mm ² / s, more preferably 75 mm ² / s, and most preferably 50 mm ² / s. On the other hand, the lower limit is preferably 1 mm ² / s, more preferably 3 mm ² / s, and most preferably 5 mm ² / s.

  The metalworking oil composition of the present invention having the above configuration is excellent in processing performance such as processing efficiency, tool life, and handling properties, and can be suitably used in a wide range of applications in the metalworking field. . The metal processing here is not limited to cutting / grinding, but broadly means general metal processing. Further, the metalworking oil composition of the present invention can be applied to metal processing by a normal oil supply system, as well as to cutting / grinding / rolling processing (MQL processing), etc., with a very small amount of oil supply.

  Specific examples of metal processing include cutting, grinding, rolling, forging, pressing, drawing, rolling, and the like. Among these, the metalworking oil composition of the present invention is very useful for applications such as cutting, grinding, and rolling, and particularly has a more remarkable effect in heavy processing, difficult processing, and difficult-to-process material processing. Demonstrate.

  Examples of heavy processing include shaving processing, deep hole processing (BTA processing, gun drill processing, etc.), broach processing, screw rolling processing, screw grinding processing, tool grinding processing, and the like.

  Examples of difficult machining include automatic lathe machining and internal turning.

  Moreover, as difficult-to-work material processing, what processes difficult-to-work materials, such as stainless steel, inconel, and hardened steel, is mentioned.

  Furthermore, the metalworking oil composition of the present invention can be used as a lubricant other than machined parts of machine tools, such as a sliding surface oil, a bearing oil, and a hydraulic equipment oil. This is very useful in that the machine can save space and energy.

  The sliding surface oil referred to in the present invention refers to a lubricating oil used in a sliding mechanism guide mechanism for two abutting surfaces among constituent members of a machine tool used for cutting and grinding. For example, in a machine tool in which a workpiece is arranged on a table movable on a bed and the table is moved to convey the workpiece to a cutting / grinding tool, The sliding surface is lubricated by the sliding surface oil. In a machine tool in which a cutting / grinding tool is fixed on a bed movable on the bed, and the tool is moved toward the workpiece by moving the table, a slide between the bed and the bed is used. The moving surface is lubricated by the sliding surface oil.

  Such sliding surface oil is required to have friction characteristics such as a low friction coefficient on the sliding surface and high stick-slip prevention. When a stick-slip occurs on a sliding surface such as a machining table of a machine tool, the frictional vibration is directly transferred to the workpiece, resulting in a decrease in machining accuracy or a decrease in tool life due to the vibration. Occurs. Although the metal composition of the present invention can sufficiently prevent these phenomena when used as a sliding surface oil, it is preferable to further contain a phosphorus compound from the viewpoint of friction characteristics. .

  In addition, there are lubricating methods such as oil bearing lubrication and mist bearing lubrication for the lubrication of the bearing portion, and the oil composition of the present invention can be used for both.

  Lubricant bearing lubrication means a lubrication system in which lubricating oil is supplied to the bearing portion in a liquid state to smoothly slide the portion, and cooling of the bearing portion with the lubricating oil can be expected. As such a lubricant for bearing lubrication, since it is used at a higher temperature part, it is required that heat deterioration hardly occurs, that is, excellent heat resistance. It can also be used for such lubricant bearing lubrication.

  Mist bearing lubrication means a lubrication system in which lubricating oil is atomized by a mist generator, and the atomized oil is supplied to the bearing part with the expectation of air or the like to smoothly slide the part. Since a cooling effect by air or the like can be expected in a high-temperature part such as a part, recent machine tools often employ this lubrication method. Such a lubricant for mist lubrication is required to be resistant to thermal deterioration because it is used at a higher temperature, that is, excellent in heat resistance. It can also be used for lubricating mist bearings.

  The hydraulic equipment performs machine operation and control by hydraulic pressure, and hydraulic hydraulic oil that is expected to have a lubricating, sealing, and cooling effect is used in the hydraulic control section that controls the operation of the machinery. Since hydraulic oil is compressed to high pressure with a pump to generate hydraulic pressure and move equipment, the lubricating oil is required to have high lubricity, high oxidation stability, and thermal stability. The oil composition can also be used for such hydraulic fluids. When the metalworking oil composition of the present invention is used as a hydraulic fluid oil, it is preferable to further contain a phosphorus compound in order to further improve the lubricity.

  Here, an example of the cutting and grinding method using the metalworking oil composition of the present invention will be described.

  FIG. 1 is an explanatory view showing an example of a machine tool suitably used in the present invention. The machine tool shown in FIG. 1 includes a table 2 that can move on the bed 1 in the direction of the arrow, and a tool 11 that is supported by the support means 10 and that can rotate in the direction of the arrow. Further, the metalworking oil composition of the present invention is accommodated in the oil supply tank 12, and when the workpiece 3 disposed on the table 2 is cut and ground, the metalworking oil composition of the present invention is used. Is supplied from the processing oil supply unit 13 toward the processing site. In addition, the metalworking oil composition of the present invention accommodated in the oil supply tank 12 is supplied from the sliding surface oil supply unit 14 to the sliding surface 16 between the bed 1 and the table 2 and is also used as a bearing oil. Supply from the supply unit 15 to the bearing unit between the support means 10 and the tool 11 causes the sliding surface 16 and the bearing unit 17 to be lubricated.

  In the above-described lubrication method, the metalworking oil composition of the present invention is used to lubricate a cutting / grinding part, a sliding surface of a machine tool, or further a bearing part, thereby improving workability in cutting / grinding. Improvement of work efficiency is achieved.

  Although not shown in detail, the metalworking oil composition of the present invention accommodated in the oil supply tank 12 can be supplied to hydraulic equipment provided in the machine tool and used as hydraulic hydraulic oil. Furthermore, the metalworking oil composition of the present invention accommodated in the oil supply tank 12 can be supplied to a gear portion included in a machine tool and used as gear oil.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

[Examples 1-22, Comparative Examples 1-2]
The metalworking oil composition shown in Table 1 was prepared using the base oils a to l and additives A to D shown below.

(1) Base oil Base oil a: THP + (iC10 + nC14) (50:50 (molar ratio)) (40 ° C. kinematic viscosity 28 mm ² / s)
Base oil b: THP + nC14 (40 ° C. kinematic viscosity 30 mm ² / s)
Base oil c: THP + nC11 (40 ° C. kinematic viscosity 24 mm ² / s)
Base oil d: THP + iC10 (40 ° C. kinematic viscosity 30 mm ² / s)
Base oil e: THP + 2EH (40 ° C. kinematic viscosity 18 mm ² / s)
Base oil f: HHP + (iC10 + nC14) (50:50 (molar ratio)) (40 ° C. kinematic viscosity 27 mm ² / s)
Base oil g: HHP + nC14 (40 ° C. kinematic viscosity 28 mm ² / s)
Base oil h: HHP + nC11 (40 ° C. kinematic viscosity 23 mm ² / s)
Base oil i: HHP + iC10 (40 ° C. kinematic viscosity 28 mm ² / s)
Base oil j: HHP + 2EH (40 ° C. kinematic viscosity 17 mm ² / s)
Base oil k: white rapeseed oil (40 ° C kinematic viscosity 36 mm ² / s)
Base oil l: SEA10 (40 ° C. kinematic viscosity 17 mm ² / s)
(However, THP is tetrahydrophthalic acid, HHP is hexahydrophthalic acid, iC10 is i-decyl alcohol, nC14 is n-tetradecyl alcohol, nC11 is n-undecyl alcohol, and 2EH is 2-ethylhexanol.)

(2) Additive Additive A: tricresyl phosphate (TCP)
Additive B: Sulfurized ester Additive C: Glycerol monooleate (GMO)
Additive D: 2,6-di-tert-butyl-p-cresol (DBPC)

  Next, the following evaluation tests were carried out using the metalworking oil compositions of Examples 1-22 and Comparative Examples 1-2.

(Tapping test)
About the metalworking oil composition of Examples 1-22 and Comparative Examples 1-2, processing performance was evaluated for diisodecyl adipate as a comparative standard oil. Specifically, a tapping test was performed under the following conditions using the metalworking oil compositions of Examples 1 to 22 or Comparative Examples 1 and 2 and diisodecyl adipate alternately. When supplying the metalworking oil composition to the processing site, the metalworking oil composition was sprayed directly on the processing site under the condition of 6 L / hour.

Tool: Nut tap M8 (P = 1.25mm)
Pilot hole diameter: φ6.8mm
Workpiece: S25C (t = 10mm)
Cutting speed: 9.0 m / min.

The tapping energy in the above test was measured, and the tapping energy efficiency (%) was calculated using the following formula.
Tapping energy efficiency (%) = (tapping energy when using comparative standard oil) / (tapping energy when using metalworking oil composition)
The obtained results are shown in Table 1. In the table, the higher the value of tapping energy efficiency, the higher the lubricity.

(Frictional property evaluation test)
Using the apparatus shown in FIG. 2, the friction characteristics of the metalworking oil compositions of Examples 1-22 and Comparative Examples 1-2 were evaluated by the following procedure.
In the apparatus shown in FIG. 2, an oil agent was dropped on the surface of the cast iron bed 1 and the cast iron table 2 that contact each other. Next, a heavy load 3 ′ is arranged on the table 2 to obtain a surface pressure of 200 kPa, and A /
The table 2 was reciprocated in the direction of the arrow by a driving means composed of a C servo meter 4, a feed screw 5 and a movable jig 6 having a bearing portion. When the table 2 was reciprocated, it was controlled by the control panel 7 and the control means 8 so that the feed speed was 400 mm / min and the feed length was 300 mm. After the table 2 is reciprocated three times in this way, the load between the table 2 and the movable jig 6 in the fourth reciprocation is measured by the load cell 9, and the table and the bed are contacted based on the obtained measurement values. The average value of the friction coefficient of the contact surface (guide surface) was obtained. The obtained results are shown in Table 1.

(Abrasion resistance evaluation test)
About the metalworking oil composition of Examples 1-22 and Comparative Examples 1-2, the abrasion test for 30 minutes was performed by rotation speed 1800rpm and load 392N by the high-speed four ball test method, and the wear scar diameter was measured. The obtained results are shown in Table 1.

(Oxidation stability test)
25 ml of a sample was placed in a 50 ml screw tube, and the amount of change in acid value was measured when heated in air at 70 ° C. for 4 weeks. The obtained results are shown in Table 1.

It is explanatory drawing which shows an example of the machine tool used suitably in the micro trace oil agent supply type cutting and grinding method of this invention. It is explanatory drawing which shows the apparatus used for the characteristic evaluation test as an oil for sliding surfaces in an Example.

Explanation of symbols

1 bed 2 table 3 work piece 3 'heavyweight 4 A / C servo meter,
DESCRIPTION OF SYMBOLS 5 Feed screw 6 Movable jig 7 Control panel 8 Control means 9 Load cell 10 Support means 11 Tool 12 Oil supply tank 13 Processing oil supply part 14 Sliding surface oil supply part 15 Bearing oil supply part 16 Sliding surface 17 Bearing part

Claims (1)

  A metal processing oil composition comprising 1 to 50% by mass of an alicyclic polyvalent carboxylic acid ester compound based on the total amount of the composition in a hydrocarbon oil.

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